Polychromophoric ultraviolet stabilizers and their use in organic compositions

ABSTRACT

The invention relates to polychromophoric compounds which have been found to be effective ultraviolet stabilizers. The invention also relates to ultraviolet degradable organic compositions containing a stabilizing amount of the polychromophoric composition to prevent such degradation. These stabilizers are effective in the presence of other additives commonly employed in polymeric compositions including, for example, pigments, colorants, fillers, reinforcing agents and the like. These ultraviolet stabilizers may also be incorporated into the organic compositions in the polymer melt or dissolved in the polymer dope, coated on the exterior of the molded article, film or extruded fiber.

This invention relates to polychromophoric ultraviolet stabilizers andtheir use in organic compositions. More particularly, the inventionrelates to polychromophoric compositions and the stabilization ofultraviolet degradable organic compositions against deteriorationresulting from the exposure to such radiations with suchpolychromophoric compositions.

The degradative effects of ultraviolet light on various organiccompositions is well known in the art. The photo-deterioration ordegradation is of particular concern with organic photo-degradablecompositions which are exposed to ultraviolet light, such as sunlight,for long periods of time. One group of such photo-degradable organiccompositions are polymeric compositions such as polyolefins, polyestersand the like. On exposure to sunlight for extended periods of time,these polymeric compositions degrade and their physical properties arereduced to render the polymeric composition less useful for mostapplications. Therefore, considerable effort has been directed toproviding a solution to the photo-degradation problem of polymericcompositions. As a result of this effort, there have been discoveredmany additives and stabilizers which improve the stability of polymericcompositions.

Moreover, various additives and stabilizers exhibit the power to absorbultraviolet radiation within the band of 2900 to 4000 A. and, whenincorporated in various plastic materials such as transparent sheets,the resultant sheet acts as a filter for all the radiation passingthrough and will transmit only such radiations as are not absorbed bythe sheet and/or the absorbing agent. It is thus possible to screen outundesirable radiations and utilize the resulting transparent sheet as afilter in many technical and commercial applications, such as wrappingsfor food products and the like.

While there are many additives, stabilizers and mixtures thereof whichare known in the art to improve the ultraviolet light stability oforganic compositions, there is a need in the art for more efficient andeffective stabilizers to prevent the photo-degradation of organiccompositions susceptible to photo-degradation. Therefore, to provide amore effective and efficient ultraviolet stabilizer for organiccompositions susceptible to such degradation would be an advance in thestate of the art.

It is, therefore, an object of the present invention to provide moreeffective and efficient ultraviolet light stabilizer compositions.

Another object of the present invention is to provide usefulcompositions characterized by improved resistance to ultravioletdegradation and deterioration.

A further object of the present invention is to provide compositionscontaining polychromophoric compositions which are resistant toultraviolet degradation.

Another and further obejct of this invention is to provide processes forimproving the resistance of organic materials to deterioration anddegradation by actinic radiation and especially ultraviolet radiation.

A still further object of this invention is to provide compositions andprocesses for improving the resistance of organic materials todeterioration and degradation by actinic radiations, including shortwave-length visible radiations.

Further objects and advantages of the invention will be apparent tothose skilled in the art from the accompanying disclosure and claims.

In accordance with the present invention, polychromophoric compositionsare provided which are useful as ultraviolet stabilizers or ultravioletscreening agents. These organic compositions contain at least oneheterocyclic group containing compositions connected to an aromaticmoiety. The polychromophoric compositions of the present invention havethe following structure: ##EQU1## wherein A is a group having thestructure ##SPC1##

R₁, R₂, R₃, R₄ and R₅ are hydrogen, hydroxy, lower alkyl or substitutedlower alkyl groups having 1 to 12 carbon atoms, cycloalkyl orsubstituted cycloalkyl, aryl or substituted aryl having 6 to 18 carbonatoms, lower alkylaryl, chloro, bromo, fluoro, alkoxy, aryloxy,substituted amino, cyano, carboalkoxy and the substituents R₁ and R₂, R₂and R₃, R₃ and R₄, and R₄ and R₅, combined with the carbon atoms towhich they are attached, are joined alkylene groups completing acarbocyclic ring, which ring can also be substituted with one or more ofthe substituents listed above for R₁, R₂, R₃, R₄ and R₅. It is necessarythat at least one of R₁ or R₅ be hydrogen, so that on exposure toultraviolet light, the heterocyclic bisphenyl ester is capable by the"Photo-Fries" rearrangement of forming a phenol group in that positionformerly joined through an oxygen atom to the carbonyl linking group.

B is a heterocyclic phenyl group having the structure ##SPC2##

wherein X and Y are a carbon atom or a nitrogen atom; Z is an oxygenatom, a sulfur atom, or a nitrogen atom containing a hydrogen atom or asubstituted or unsubstituted lower alkyl group having 1 to 12 carbonatoms; I is hydrogen, fluoro, chloro, bromo, lower alkyl, substitutedlower alkyl, cycloalkyl, substituted cycloalkyl, aryl substituted aryl,lower alkylaryl, alkoxy, aryloxy, substituted amino, and cyano. I ispresent on all positions of the benzenoid ring, except the carbon atomattached to the heterocyclic ring and the carbon atom attached to thecarbonyloxy or oxycarbonyl group. When the heterocyclic bisphenyl esteris structure II, it is necessary that at least one of I, ortho to thecarbon atom attached to oxycarbonyl group be hydrogen, so that onexposure to ultraviolet light, the heterocyclic bisphenyl ester iscapable by the "Photo-Fries" rearrangement of forming a phenol group inthat position formerly joined through an oxygen atom to the carbonyllinkage group.

E is substituted or unsubstituted alkylene and arylene; n is an integerfrom 1 to 6.

Suitable A groups are phenyl, naphthyl, 2,4-di-t-butylphenyl,2-t-butyl-4-methylphenyl, 3-methoxyphenyl, 3-chlorophenyl,4-acetamidophenyl, 4-carbomethoxyphenyl and the like.

Suitable B groups are, for example, moieties having the structure:##SPC3##

and include substituted and unsubstituted 1,3,4-oxadiazol-2,5-diyl,1,3,4-thiadiazol-2,5-diyl, 1,2,4-triazol-3,5-diyl, oxazol-diyl,thiazoldiyl and imidazol-diyl and the like.

Examples of suitable 1,3,4-oxadiazol-2,5-diyl moieties are those havingthe structures: ##SPC4##

wherein E is a substituted or unsubstituted alkylene having 1 to 12carbon atoms or arylene having 6 to 18 carbon atoms; n is an integerfrom 1 to 6; such as 4,4'-(1,3,4-oxadiazol-2,5-diyl)diphenyl,4,4'[5,5'-tetramethylene bis(1,3,4-oxadiazol-2-yl)]diphenyl,4,4'-[5,5'-bis(1,3,4-oxadiazol-2,2'-diyl)diphenyl,4,4'-[5,5'-m-phenylene bis(1,3,4-oxadiazol-2-yl)]diphenyl,4,4',4"-[5,5',5"-(1,3,5-phenylene)tris(1,3,4-oxadiazol-2-yl)triphenyland the like.

Examples of suitable 1,3,4-thiadiazol-2,5-diyl moieties are those havingthe structures: ##SPC5##

wherein E is a substituted or unsubstituted alkylene or arylene; n is aninteger from 1 to 6; such as 4,4'-(1,3,4-thiazol-2,5-diyl)diphenyl,4,4'-[5,5'-tetramethylene bis(1,3,4-thiadiazol-2-yl)]diphenyl,4,4'-[5,5'-bis(1,3,4-thiadiazol-2,2'-diyl)]diphenyl,4,4'-[5,5'-m-phenylene bis(1,3,4-thiadiazol-2-yl)]diphenyl,4,4',4"-[5,5',5"-(1,3,5-phenylene)tris(1,3,4-oxadiazol-2-yl)]triphenyland the like.

Examples of suitable 1,2,4-triazol-3,5-diyl moieties are those havingthe structures: ##SPC6##

wherein E is a substituted or unsubstituted alkylene and arylene; n isan integer from 1 to 6, Q is hydrogen or a substituted or unsubstitutedlower alkyl group containing 1 to 12 carbon atoms; such as4,4'-(1H-1,2,4-triazol-3,5-diyl)diphenyl,4,4'(4H-1,2,4-triazol-3,5-diyl)diphenyl, 4,4'-[5,5'-tetramethylenebis(4H-1,2,4-triazol-3-yl)]diphenyl,4,4'-(4-methyl-1,2,4-triazol-3,5-diyl)diphenyl,4,4'-(1-methyl-1,2,4-triazol-3,5-diyl)diphenyl, 4,4'-[5,5'-m-phenylenebis(4-methyl-1,2,4-triazol-3-yl)]diphenyl, and the like.

Examples of suitable oxazol-diyl moieties are those having thestructures: ##SPC7##

wherein E is a substituted or unsubstituted alkylene and arylene, or thesame as R₁ ; J is the same as R₁ or a substituted or unsubstitutedalkylene having 1 to 12 carbon atoms or arylene having 6 to 18 carbonatoms; n is an integer from 1 to 6; such as4,4'-(oxazol-2,5-diyl)diphenyl, 4,4'-(4-methyloxazol-2,5-diyl)diphenyl,4,4'-(4-phenyloxazol-4,5-diyl)diphenyl,3,4'-(4-methyloxazol-2,5-diyl)diphenyl and the like.

Examples of suitable thiazol-diyl moieties are those having thestructures: ##SPC8##

wherein E is a substituted or unsubstituted alkylene and arylene, or thesame as R₁ ; J is the same as R₁ or a substituted or unsubstitutedalkylene or arylene; n is an integer from 1 to 6; such as4,4'-(thiazol-2,5-diyl)diphenyl,4,4'-(4-methylthiazol-2,5-diyl)diphenyl,4,4'-(2-methylthiazol-4,5-diyl)diphenyl,4,4'-(thiazol-4,5-diyl)diphenyl, and the like.

Examples of suitable imidazol-diyl moieties are those having thestructures: ##SPC9##

wherein E is a substituted or unsubstituted alkylene and arylene, or thesame as R_(1J) is the same as R₁, or a substituted or unsubstitutedalkylene or arylene; n is an integer from 1 to 6; Q is hydrogen or asubstituted or unsubstituted lower alkyl group having 1 to 12 carbonatoms, such as 4,4'-(imidazol-2,5-diyl)diphenyl,4,4'-(1-methylimidazol-2,5-diyl)diphenyl,4,4'-(2-methylimidazol-4,5-diyl)diphenyl,4,4'-(4-methylimidazol-2,5-diyl)diphenyl,4,4'-(1,4-dimethylimidazol-2,5-diyl)diphenyl and4,4'-(1,2-dimethylimidazol-4,5-diyl)diphenyl and the like.

The heterocyclic compositions can be added to organic compositions whichare susceptible to ultraviolet degradation. Such compositions include,for example, polymeric compositions such as polyester fiber and moldingcompositions, such as polyethylene terephthalate, polytetramethyleneterephthalate and the like; polyolefins such as, for example, high,medium and low density polyethylene, polypropylene, polybutene and thelike; polyamides such as N-methoxymethyl polyhexamethylene adipamide,nylon 66 and the like; polycarbonates; poly(vinyl chlorides) andcopolymers; cellulose esters; acrylic/butadiene/styrene plastic;polyacrylics such as methyl methacrylate; polystyrene; gelatin;vinylidene chloride copolymers such as vinylidene chloride/vinyl acetatecopolymers; ethylene vinyl acetate copolymers; cellulose ethers such asmethyl cellulose; polyvinyl esters such as polyvinyl acetate;polyethylene oxide; polyvinyl acetals; polyformaldehydes; andpolyurethanes. Such compositions also include natural and syntheticrubbers, such as polybutadiene, and unsaturated organic compositionssuch as oils and the like, as well as compositions containing suchorganic compositions.

The polychromophoric compositions, as effective ultraviolet stabilizersor screening agents, are generally used in an amount of from 0.01 to10%, by weight, based on the weight of the organic material to whichthey are added. While a detectable amount of ultraviolet screening andstabilization may be obtained with amounts less than 0.01%, this amountof stabilization or screening would be of little practical utility in acommercial application. Moreover, while amounts greater than 10% byweight provide effective ultraviolet stability and screening, suchconcentrations are undesirable because of cost and the deleteriouseffect which such concentrations may have on the mechanical propertiesof the organic composition in which the stabilizer is incorporated.Preferably, the stabilizer is used in an amount of from about 0.1 toabout 3%, by weight. For example, an amount of 2%, by weight, of thestabilizer effectively stabilizes cellulose acetate butyrate plasticcompositions.

The ultraviolet stabilized organic compositions of the present inventionmay also contain other additives, pigments, colorants, stabilizers andthe like. For example, polymeric compositions, such as polyolefins, mayalso contain and generally do contain other additives such as white orcolored pigments or colorants, antioxidants, plasticizers, flow aids,processing aids, polymeric modifiers and the like.

These novel polychromophoric ultraviolet stabilizers may be incorporatedinto organic compositions by melt-blending or may be added onto thesurface of an organic plastic material prior to being molded into asuitable object. These materials can also be added to coatings and thelike which can be applied to the surface of a molded object.

This invention will be further illustrated by the following examplesalthough it will be understood that these examples are included merelyfor purposes of illustration and are not intended to limit the scope ofthe invention.

EXAMPLE 1

Diphenyl-4,4'-(1,3,4-oxadiazol-2,5-diyl)dibenzoate, (I) can be preparedby the following procedure:

To a solution of hydrazine (0.01 mole) and sodium bicarbonate (15 g.) in150 ml. of water, monoterephthaloyl chloride (0.18 mole) in 125 ml. ofTHF was added slowly with stirring. After stirring for an additional 30minutes, the Product A was filtered and washed with 1 liter of water(m.p. 295°-8°, quantitative yield). A solution of A (0.056 mole) and 100ml. of phosphorus oxychloride in 200 ml. of toluene was refluxed for 6hours. The product B was filtered ans washed with water (m.p. 268°-270°,yield 80%). A solution of B (0.042 mole) and potassium hydroxide (0.1mole) in 700 ml. of 60% ethanol was refluxed for 10 hours. The mixturewas then acidified with 6N HCl. The product was filtered and identifiedas the corresponding bis acid (m.p. >300°, quantitative yield). The bisacid (0.013 mole) was refluxed with 50 ml. of thionyl chloride in 200ml. of chlorobenzene for 10 hours. After removal of excess thionylchloride, the product C was obtained by filtration (m.p. 208°-210°,yield 90%). To a solution of phenol (0.036 mole) and sodium hydroxide(0.025 mole) in 50 ml. of water, C (0.012 mole) in 150 ml. of chloroformwas added. The mixture was refluxed for 4 hours. After cooling, ProductI was obtained by filtration (m.p. 275°-280°, yield 50%). ##SPC10##

EXAMPLE 2

Bis(m-hydroxyphenyl)4,4'-(1,3,4-oxadiazol-2,5-diyl)dibenzoate, (II) canbe prepared by following the same procedure as described in Example 1(m.p. >300°, yield 50%).

EXAMPLE 3

Diphenyl-4,4'-(1,3,4-thiadiazol-2,5-diyl)dibenzoate, (III) can beprepared by the following procedure:

1,2-di(4-Carbomethoxybenzoyl)hydrazine (A), prepared as in Example 1, inpyridine was refluxed with phosphorus pentasulfide for 15 hours. Themixture was cooled and poured into 20% ethanol. After the solution wasneutralized with sodium bicarbonate, the product,dimethyl-4,4'-(1,3,4-thiadiazol-2,5-diyl)dibenzoate (D), was obtained byfiltration (m.p. 268°-270°, yiled 60%). Then III was obtained byreacting D in a similar manner as in Example 1 (m.p. >300°, 60%).

EXAMPLE 4

Diphenyl-4,4'-(4-methyl-1,2,4-triazol-3,5-diyl)dibenzoate (IV) can beprepared by the following procedure:

A solution of N-methyl-p-carbmethoxybenzamide in chloroform was treatedwith phosphorus pentachloride to give E. Then E was reacted withp-carbmethoxybenzoyl hydrazine to yielddimethyl-4,4'-(4-methyl-1,2,4-triazol-3,5-diyl)dibenzoate, (F). Then IVwas obtained by reacting F in a similar manner as in Example 1.

EXAMPLE 5

Diphenyl-4,4'-(5,5'-bi-1,3,4-oxadiazol-2,2'-diyl)dibenzoate, (V) can beprepared by the following procedure:

A mixture of oxalyl dihydrazine (0.01 mole), lithium chloride (2.0 g)and p-carbmethoxybenzoyl chloride (0.02 mole) in N-methyl pyrrolidinone(100 ml.) was stirred at room temperature overnight. The mixture waspoured into 500 ml. of ice-water. The product,1,1'-oxalylbis[2-(p-carbmethoxybenzoyl hydrazine], G, was obtained byfiltration. Then V was produced by reacting G in a similar manner as inExample 1 (m.p. >300°, 50%).

EXAMPLE 6

2,5-Bis(p-benzoyloxyphenyl)-1,3,4-oxadiazole (VI) can be prepared by thefollowing procedure: ##SPC11##

p-Hydroxybenzoic acid was refluxed with benzoyl chloride for 4 hours togive A'. A' was heated with excess thionyl chloride for 2 hours to yieldB'. B' (0.1 mole) in 100 ml. N-methylpyrrolidinone was treated with .03mol. 60% hydrazine in 50 ml. N-methylpyrrolidinone for 1 hour at 5°-10°and then stirred an additional hour at room temperature. The mixture waspoured into 500 ml. ice-water and filtered to obtain C'. The mixture ofC' and excess thionyl chloride was refluxed for 2 hours. After removalof thionyl chloride, the product VI, was obtained and recrystallizedfrom toluene (m.p. 200°-3°, yield 70%).

EXAMPLE 7

Diphenyl-4,4'-(4-methyloxazol-2,5-diyl)dibenzoate (VII) can be producedby the following procedure:

α-(p-Carbomethoxybenzamido)-p-carbmethoxypropiophenone, obtained byreaction of p-carbmethoxybenzamide andα-bromo-p-carbmethoxypropiophenone, was refluxed in toluene withphosphorus oxychloride to yield 70%dimethyl-4,4'-(4-methyloxazol-2,5-diyl)dibenzoate, D'. Then VII wasobtained in a similar manner as in Example 1.

EXAMPLE 8

Diphenyl-4,4'-(2-methyloxazol-4,5-diyl)dibenzoate (VIII) can be producedby the following procedure:

p,p'-Dicarbmethoxybenzoin, obtained by benzoin condensation of methylp-formylbenzoate, was refluxed with ammonium acetate, paraldehyde inglacial arctic acid for 2 hours. The product,dimethyl-4,4'-(2-methyloxazol-4,5-diyl)dibenzoate, E', was obtained byfiltration after cooling. Then VIII was obtained in a similar manner asin Example 1.

EXAMPLE 9

The ultraviolet stabilization provided by the heterocyclic stabilizer ofthe present invention is shown for poly(tetramethylene terephthalate) inTable 1.

A dry mixture of the stabilizer and granulated poly(tetramethyleneterephthalate) was extruded into 1/16 in. diam. rods, pelletized andinjection molded into 21/2- × 1/2- × 1/16-inch flat bars; these flatbars were exposed to a 280-700 nm. mercury lamp. The test results aresummarized in Table 1.

                  Table 1                                                         ______________________________________                                        Effectiveness of Ultraviolet Stabilizers                                      in Poly(tetramethylene terephthalate)                                                   FWIS (Flatwise Impact Strength)                                     Compound (0.5%)                                                                           Initial    300 hr.    500 hr.                                     ______________________________________                                        None            17          6        1                                        I               20         20       18                                        II              20         19       20                                        III             18         18       16                                        IV              19         17       15                                        V               20         20       20                                        VI              19         17       17                                        VII             17         17       15                                        VIII            18         16       14                                        ______________________________________                                    

These polychromophoric compositions find particular utility asultraviolet stabilizers in organic compositions requiring ultravioletstability. Such compositions include polymeric compositions such as, forexample, polyester fiber and molding compositions, poly-α-olefins,polyamides, acrylics, cellulose esters and the like, as well as moldedor shaped articles, film and coatings formed from such materials and thelike. Such compositions also include natural and synthetic rubbers, aswell as organic materials such as oils, fats, and unsaturated organicmaterials and materials having such materials contained therein such aspaints, varnishes, cosmetics and the like.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:
 1. An organic composition susceptible to ultravioletdegradation stabilized against such degradation with a stabilizingamount of a composition of matter comprising compounds having theformula: ##EQU2## wherein A is a group having the structure:##SPC12##wherein R₁, r₂, r₃, r₄ and R₅ are hydrogen, hydroxy, chloro,bromo, fluoro, lower alkyl, substituted lower alkyl, cycloalkyl,substituted cycloalkyl, aryl, substituted aryl, lower alkylaryl, alkoxy,aryloxy, amino, substituted amino, cyano, carboalkoxy and thesubstituents R₁ and R₂, R₂ and R₃, R₃ and R₄, and R₄ and R₅ combinedwith the carbon atoms to which they are attached, are joined alkylenegroups completing a carbocyclic ring, which ring can also be substitutedwith one or more of the substituents listed above for R₁, R₂, R₃, R₄ andR₅ ; B is a heterocyclic group having the structures ##SPC13## wherein Xand Y are a carbon atom, a carbon atom containing an alkyl group having1 to 12 carbon atoms, a carbon atom containing an aryl group having 6 to18 carbon atoms or a nitrogen atom; Z is an oxygen atom, a sulfur atom,or a nitrogen atom containing a hydrogen atom or a substituted orunsubstituted lower alkyl group having 1 to 12 carbon atoms; I ishydrogen, chloro, bromo, fluoro, lower alkyl, substituted lower alkyl,cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, loweralkylaryl, aryl-substituted-aryl, alkoxy, aryloxy, substituted amino andcyano, said I is present on all positions of the benzenoid ring, exceptthe carbon atom attached to the heterocyclic ring and the carbon atomattached to the carbonyloxy or oxycarbonyl group, E is a substituted orunsubstituted alkylene and arylene and n is an integer from 1 to 6wherein at least one of R₁, R₅ or I ortho to the oxy of said carbonyloxyor oxycarbonyl group is hydrogen.
 2. An organic composition susceptibleto ultraviolet degradation stabilized against such degradation with astabilizing amount of a composition of matter according to claim 1having the formula ##SPC14##R₁, r₂, r₃, r₄ and R₅ are hydrogen, hydroxy,chloro, bromo, fluoro, lower alkyl, substituted lower alkyl, cycloalkyl,substituted cycloalkyl, aryl, substituted aryl, lower alkylaryl, alkoxy,aryloxy, substituted amino, cyano, carboalkoxy and the substituents R₁and R₂, R₂ and R₃, R₃ and R₄, and R₄ and R₅ combined with the carbonatoms to which they are attached, are joined alkylene groups completinga carbocyclic ring, which ring can also be substituted with one or moreof the substituents listed above the R₁, R₂, R₃, R₄ and R₅ ; D iscarbonyloxy or oxycarbonyl; Z is an oxygen atom, a sulfur atom, or anitrogen atom containing a hydrogen atom or a substituted orunsubstituted lower alkyl group having 1 to 12 carbon atoms; I ishydrogen, chloro, bromo, fluoro, lower alkyl, substituted lower alkyl,cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, loweralkylaryl, aryl-substituted-aryl, alkoxy, aryloxy, substituted amino andcyano, and I is present on all positions of the benzenoid ring, exceptthe carbon atom attached to the heterocyclic ring and the carbon atomattached to the carbonyloxy or oxycarbonyl group, E is a substituted orunsubstituted alkylene and arylene and n is an integer from 1 to 6wherein at least one of R₁, R₅ or I ortho to the oxy of said carbonyloxyor oxycarbonyl group is hydrogen.
 3. An organic composition susceptibleto ultraviolet degradation stabilized against such degradation with astabilizing amount of a composition of matter according to claim 1having the formula ##SPC15##R₁, r₂, r₃, r₄, r₅, and R₆ are hydrogen,hydroxy, chloro, bromo, fluoro, lower alkyl, substituted lower alkyl,cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, loweralkylaryl, alkoxy, aryloxy, amino, substituted amino, cyano,carboalkoxy, and the substituents R₁ and R₂, R₂ and R₃, R₃ and R₄, andR₄ and R₅ combined with the carbon atoms to which they are attached, arejoined alkylene groups completing a carbocyclic ring, which ring canalso be substituted with one or more of the substituents listed abovefor R₁, R₂, R₃, R₄, R₅ and R₆ ; D is carbonyloxy or oxycarbonyl; Z is anoxygen atom, a sulfur atom, or a nitrogen atom containing a hydrogenatom or a substituted or unsubstituted lower alkyl group having 1 to 12carbon atoms; I is hydrogen, chloro, bromo, fluoro, lower alkyl,substituted lower alkyl, cycloalkyl, substituted cycloalkyl, aryl,substituted amino and cyano, said I is present on all positions of thebenzenoid ring, except the carbon atom attached to the heterocyclic ringand the carbon atom attached to the carbonyloxy or oxycarbonyl group; Eis a substituted or unsubstituted alkylene and arylene and n is aninteger from 1 to 6 wherein at least one of R₁, R₅ or I ortho to the oxyof said carbonyloxy or oxycarbonyl group is hydrogen.
 4. An organiccomposition susceptible to ultraviolet degradation stabilized againstsuch degradation with a stabilizing amount of a composition of matteraccording to claim 1 having the formula ##SPC16##R₁, r₂, r₃, r₄, r₅ andR₆ are hydrogen, hydroxy, chloro, bromo, fluoro, lower alkyl,substituted lower alkyl, cycloalkyl, substituted cycloalkyl, aryl,substituted aryl, lower alkylaryl, alkoxy, aryloxy, amino, substitutedamino, cyano, carboalkoxy, and the substituents R₁ and R₂, R₂ and R₃, R₃and R₄, and R₄ and R₅ combined with the carbon atoms to which they areattached, are joined alkylene groups completing a carbocyclic ring,which ring can also be substituted with one or more of the substituentslisted above for R₁, R₂, R₃, R₄, R₅ and R₆ ; D is carbonyloxy oroxycarbonyl; Z is an oxygen atom, a sulfur atom, or a nitrogen atomcontaining a hydrogen atom or a substituted or unsubstituted lower alkylgroup having 1 to 12 carbon atoms; I is hydrogen, chloro, bromo, fluoro,lower alkyl, substituted lower alkyl, cycloalkyl, substitutedcycloalkyl, aryl, substituted amino and cyano, said I is present on allpositions of the benzenoid ring, except the carbon atom attached to theheterocyclic ring and the carbon atom attached to the carbonyloxy oroxycarbonyl group; E is a substituted or unsubstituted alkylene andarylene and n is an integer from 1 to 6 wherein at least one of R₁, R₅or I ortho to the oxy of said carbonyloxy or oxycarbonyl group ishydrogen.
 5. An organic composition according to claim 2 containing astabilizing amount of a compound having the formula: ##SPC17##
 6. Anorganic composition according to claim 2 containing a stabilizing amountof a compound having the formula: ##SPC18##
 7. An organic compositionaccording to claim 2 containing a stabilizing amount of a compoundhaving the formula: ##SPC19##
 8. An organic composition according toclaim 2 containing a stabilizing amount of a compound having theformula: ##SPC20##
 9. An organic composition according to claim 2containing a stabilizing amount of a compound having the formula:##SPC21##
 10. An organic composition according to claim 2 containing astabilizing amount of a compound having the formula: ##SPC22##
 11. Anorganic composition according to claim 2 containing a stabilizing amountof a compound having the formula: ##SPC23##
 12. An organic compositionaccording to claim 2 containing a stabilizing amount of a compoundhaving the formula: ##SPC24##
 13. An organic composition according toclaim 2 containing a stabilizing amount of a compound having theformula: ##SPC25##
 14. An organic composition according to claim 2containing a stabilizing amount of a compound having the formula:##SPC26##
 15. An organic composition according to claim 2 containing astabilizing amount of a compound having the formula: ##SPC27##
 16. Anorganic composition according to claim 2 containing a stabilizing amountof a compound having the formula: ##SPC28##
 17. An organic compositionaccording to claim 2 containing a stabilizing amount of a compoundhaving the formula: ##SPC29##
 18. An organic composition according toclaim 2 containing a stabilizing amount of a compound having theformula: ##SPC30##
 19. An organic composition according to claim 2containing a stabilizing amount of a compound having the formula:##SPC31##
 20. An organic composition according to claim 2 containing astabilizing amount of a compound having the formula: ##SPC32##
 21. Anorganic composition according to claim 2 containing a stabilizing amountof a compound having the formula: ##SPC33##
 22. An organic compositionaccording to claim 2 containing a stabilizing amount of a compoundhaving the formula: ##SPC34##
 23. An organic composition according toclaim 2 containing a stabilizing amount of a compound having theformula: ##SPC35##
 24. An organic composition according to claim 3containing a stabilizing amount of a compound having the formula:##SPC36##
 25. An organic composition according to claim 3 containing astabilizing amount of a compound having the formula: ##SPC37##
 26. Anorganic composition according to claim 3 containing a stabilizing amountof a compound having the formula: ##SPC38##
 27. An organic compositionaccording to claim 3 containing a stabilizing amount of a compoundhaving the formula: ##SPC39##
 28. An organic composition according toclaim 3 containing a stabilizing amount of a compound having theformula: ##SPC40##
 29. An organic composition according to claim 3containing a stabilizing amount of a compound having the formula:##SPC41##
 30. An organic composition according to claim 4 containing astabilizing amount of a compound having the formula: ##SPC42##